CN110721597B - Method for simply preparing porous membrane with excellent connectivity - Google Patents
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- CN110721597B CN110721597B CN201910926764.6A CN201910926764A CN110721597B CN 110721597 B CN110721597 B CN 110721597B CN 201910926764 A CN201910926764 A CN 201910926764A CN 110721597 B CN110721597 B CN 110721597B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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Abstract
The invention discloses a method for simply preparing a porous membrane with excellent connectivity, which takes a fluorine-containing polymer as a base material, a water-soluble high molecular weight polymer which can be taken as a pore-foaming agent as a template agent, a high-boiling-point organic solvent as a diluent and adopts a thermally induced phase separation technology to prepare the porous membrane of the fluorine-containing polymer. The invention has the characteristics of simple preparation process, good porous membrane through performance and adjustable micropores.
Description
Technical Field
The invention relates to a preparation method of a porous membrane, in particular to a method for simply preparing a porous membrane with excellent penetration.
Background
As a new separation technique developed in recent years, a fluorine-containing polymer such as polyvinylidene fluoride is a material which is currently widely used for preparing a porous membrane, and is widely used in the fields of water treatment (such as pretreatment of nanofiltration, reverse osmosis, turbidity removal of surface water, treatment of production domestic sewage, and the like) and membrane contactors (such as membrane absorption, membrane extraction, and the like). The membrane has higher flux, which is a precondition for the practical value of the membrane for water treatment (especially microfiltration and ultrafiltration membranes). The lower the filtration resistance, the higher the flux. The improvement of the membrane pore connectivity is a main factor for reducing the filtration resistance of the membrane, and the membrane pore connectivity can be remarkably improved by adopting a template method, for example, nano calcium carbonate is added into a polymer solution, the nano calcium carbonate is dissolved by hydrochloric acid after membrane formation, and the connectivity among membrane pores is improved by the space occupied by the nano calcium carbonate. However, in the process of film formation by the phase inversion technique, no matter the material mixing and defoaming process in the film formation process by the non-solvent induced phase technique (NIPS) or the material mixing process by the thermal induced phase separation Technique (TIPS), the method of physically doping inorganic nanoparticles cannot avoid the problems of agglomeration of the inorganic nanoparticles and uneven dispersion in the film. The agglomeration of inorganic nanoparticles increases the defects of the membrane, not only widens the pore distribution of the membrane and deteriorates the filtration precision, but also significantly reduces the mechanical properties of the membrane, and the agglomeration is deteriorated with the increase of the addition amount of the inorganic nanoparticles, so that the upper limit of the addition amount of the inorganic nanoparticles is usually only 3%. Therefore, how to avoid the agglomeration of the inorganic nanoparticles, improve the uniformity of the size thereof, and the uniformity of the dispersion thereof in the film is a key point for effectively solving the problem.
The principle of TIPS membrane formation is as follows: the polymer and a specific diluent are formed into a solution (generally called casting solution) at a high temperature, when the temperature is reduced, because the dissolving capacity of the diluent for the polymer is reduced, phase separation (solid-liquid or liquid-liquid phase separation) occurs between the polymer and the diluent in the casting solution, and after the diluent is removed by extraction, micropores are formed in the space occupied by the diluent in the casting solution. The TIPS technology generally can obtain a spherical particle structure formed through solid-liquid phase separation, a closed honeycomb pore structure formed through liquid-liquid phase separation, and a through-network pore structure formed through spinodal phase separation, wherein the honeycomb pores are closed structures and are not suitable for being used as separation membranes. Compared with the NIPS technology, the TIPS technology has the advantages of easy regulation and control of membrane pore structure, high membrane strength, dry-state preservation of the membrane and the like, is particularly suitable for preparing the polymer porous membrane without proper solvent at room temperature, and the polyethylene, polypropylene and polyvinylidene fluoride porous membranes are prepared by adopting the method at present. However, in the TIPS technology, since the temperature of the casting film liquid is greatly different from the temperature of the coagulation bath in the film forming process, a thick compact skin layer is easily generated on the outer surface of the film when the outer surface of the film is cooled by water, so that the filtration resistance of the film is remarkably increased, and the flux of the film is remarkably reduced. Therefore, in order to solve the above problems, it is necessary to develop a hollow fiber membrane with a porous non-compact outer skin layer, which has uniform pore diameter and adjustable size, by the TIPS technology.
Disclosure of Invention
The invention aims to provide a method for simply preparing a porous membrane with excellent penetrability. The invention has the characteristics of simple preparation process, good porous membrane through performance and adjustable micropores.
The technical scheme of the invention is as follows: a method for simply preparing a porous membrane with excellent connectivity uses a fluorine-containing polymer as a base material, a water-soluble high molecular weight polymer which can be used as a pore-foaming agent as a template agent, a high boiling point organic solvent as a diluent, and a TIPS technology to prepare the porous membrane of the fluorine-containing polymer.
The method for simply preparing the porous membrane with excellent penetration property comprises the following specific steps:
s1, taking a fluorine-containing polymer, a water-soluble high molecular weight polymer, a diluent and an antioxidant, wherein the mass ratio of the fluorine-containing polymer to the water-soluble high molecular weight polymer to the diluent to the antioxidant is 20-30: 2-10: 59.9-77.9: 0.1-1, mixing in a mixer, extruding by an extruder, and cooling in air for granulation;
s2, melting the obtained mixture particles and scraping the mixture particles into a film at the temperature of 100-150 ℃, cooling and solidifying the film by air, and then further cooling and forming the film in water at room temperature;
and S3, taking out the film, soaking and washing the film by using a room-temperature extracting agent, washing to remove the diluent and the water-soluble high-molecular-weight polymer, taking out the film, airing, and carrying out heat setting treatment.
In the simple method for producing a porous film having excellent permeability, in step S1, the mass ratio of the fluoropolymer to the water-soluble high molecular weight polymer to the diluent to the antioxidant is 25: 6: 68.9: 0.5.
in the above-described method for easily producing a porous film having excellent permeability, the fluoropolymer in step S1 is a homopolymer or copolymer of polyvinylidene fluoride.
In the simple method for preparing a porous membrane with excellent permeability, the water-soluble high molecular weight polymer in step S1 is one of polyvinylpyrrolidone and polyethylene glycol with a molecular weight of not less than 1000.
In the above simple method for preparing a porous membrane with excellent permeability, the diluent in step S1 is one of dibutyl sebacate, tributyrin and ethylene carbonate organic matter.
In the simple method for producing a porous film having excellent permeability, the antioxidant in step S1 is octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In the simple method for preparing the porous membrane with excellent penetrability, the scraping speed of the scraping membrane in the step S2 is 10mm-2m/min, and the cooling time in the air is 15-30S.
In the simple method for preparing the porous membrane with excellent permeability, the extractant in step S3 is absolute ethyl alcohol or deionized water, and the number of washing times is 2, and each washing time is 1 hour.
In the simple method for preparing the porous membrane with excellent connectivity, the heating and setting temperature in step S3 is 80-130 ℃, and the time is 10-30 min.
The invention has the advantages of
The principle of the invention for preparing the high-flux porous membrane is as follows: some of the diluents used in TIPS technology dissolve the polymer and some of the water soluble high molecular weight polymer at high temperatures, while at room temperature both the polymer and the water soluble high molecular weight polymer solidify out of the diluents, leaving space after subsequent extraction of the water soluble high molecular weight polymer with water to further improve pore penetration. Compared with the prior art that inorganic nanoparticles such as nano calcium carbonate and the like which are physically doped cannot be dissolved in the diluent at room temperature and high temperature, the water-soluble high molecular weight polymer can be dissolved in the diluent at high temperature but cannot be dissolved in the diluent at room temperature, and the solidification and precipitation of the water-soluble high molecular weight polymer occur in the process of cooling. Because the solidification process of the water-soluble high molecular weight polymer is uniformly carried out in the process of cooling, the phenomena of nonuniform mixing and agglomeration of the traditional doped inorganic nano particles can not occur. Because the thickness of the polymer solution is very thin, the uniformity of the cooling and heat transfer process can be ensured, and finally the water-soluble high molecular weight polymer is solidified in the diluent to form the polymer which has uniform size, adjustable size within a certain range (5-300 nm), no agglomeration phenomenon and uniform distribution in the base material polymer. The space left by the water-soluble high molecular weight polymer after extraction can obviously improve the connectivity of membrane pores, thereby obviously improving the membrane flux. That is, the pore size and flux of the membrane can be easily adjusted by adjusting the type and amount of the water-soluble high molecular weight polymer. In addition, the water-soluble high molecular weight polymer is extracted by water, so that a certain amount of acidic wastewater generated by removing nano calcium carbonate by using acid in the prior art is avoided. The solubility of different kinds of water-soluble high molecular weight polymers in a diluent at high temperature is 8-30% (based on 100 parts of the diluent, and the solubility of the water-soluble high molecular weight polymers in the diluent is not greatly changed in the range of 100-150 ℃, and the addition of the polymers hardly influences the solubility of the water-soluble high molecular weight polymers in the diluent), and experiments prove that the membrane flux can be obviously improved when the addition amount of the water-soluble high molecular weight polymers reaches 3 parts (based on 70 parts of the diluent and 27 parts of the polymers), namely, the membrane pore penetration is enough to be improved. And the method is irrelevant to the membrane structure prepared by TIPS without adding water-soluble high molecular weight polymer, namely, the method can obviously improve the connectivity of membrane pores regardless of a spherical particle structure, a closed honeycomb pore structure and a reticular pore structure. The inorganic salt chloride which is subjected to temperature reduction crystallization and can be used as a template agent needs to meet the following conditions: (1) the water-soluble high molecular weight polymer has certain solubility in the diluent under the condition of high temperature (not less than 5 parts in 100 parts of the diluent) but can not be dissolved in the diluent at room temperature, so that the effects of solidifying and separating out the water-soluble high molecular weight polymer in the quenching process and improving the connectivity of film pores by the water-soluble high molecular weight polymer template agent can be ensured. Polyethylene glycol with molecular weight less than 1000 can not be solidified and separated out in diluent, and polyvinylpyrrolidone with weight average molecular weight not less than 3.1 ten thousand is all suitable. The solubility of polyvinylpyrrolidone in diluent is higher than that of polyethylene glycol, and the solubility of the same kind of water-soluble high molecular weight polymer in diluent is slightly reduced along with the increase of molecular weight. In addition, the water-soluble high molecular weight polymer does not achieve the above-mentioned effects in a conventional diluent such as dibutyl phthalate. (2) The water-soluble high molecular weight polymer is required to have good thermal stability so as to prevent the water-soluble high molecular weight polymer from decomposing at high temperature and losing the curing property. (3) The blending amount of the water-soluble high molecular weight polymer is not required to be excessive (the purpose of remarkably improving the flux can be achieved by blending a proper amount), the proper size of the solidified and precipitated water-soluble high molecular weight polymer is ensured, the size of the finally formed membrane pore is not required to be excessive, and the filtration precision of the membrane is not reduced. (4) The scraped film casting solution stays in the air for 15-30S to ensure that the film casting solution is subjected to phase splitting and the water-soluble high molecular weight polymer is cured, and then the film casting solution is further cured and formed in condensed room temperature water. If the retention time is too short (less than 15S), the water enters the water at room temperature, and the cooling rate of the water is much higher than that of the air, so that on one hand, the water-soluble high molecular weight polymer is solidified too fast, solidified and grown insufficiently, and the final pore size of the film is too small; on the other hand, the water-soluble high molecular weight polymer at the surface dissolves in water and the rapid heat and mass transfer between water and diluent results in a dense thick skin layer, eventually losing the effect of the water-soluble high molecular weight polymer templating agent. And ensuring the film casting solution to have a residence time of 15-30S in the air is easy to realize for a film scraping device.
The invention has the advantages that: (1) the preparation process is simple. The high-flux membrane product can be prepared by only using the equipment for preparing the flat membrane by using the existing commercial TIPS technology without adding any additional equipment and operation steps. (2) The improvement of the membrane pore connectivity and the flux effect are obvious and simple to realize: the thickness of the polymer solution is very thin, so that the uniformity of the cooling and heat transfer process can be ensured, and finally, the water-soluble high molecular weight polymer is solidified in the diluent to form the polymer which has uniform size, adjustable size within a certain range, no agglomeration phenomenon and uniform distribution in the base material polymer. The space left by the water-soluble high molecular weight polymer after extraction can obviously improve the connectivity of membrane pores, thereby obviously improving the membrane flux. That is, the pore size and flux of the membrane can be easily adjusted by adjusting the type and amount of the water-soluble high molecular weight polymer. Because the water-soluble high molecular weight polymer is uniformly solidified and separated out in the process of cooling, the phenomena of nonuniform mixing and agglomeration caused by the traditional doping of inorganic nano particles can not occur. (3) Adjustment of the microstructure of the film: the water-soluble high molecular weight polymer is used as a template agent, and can improve the surface porosity of the membrane and the connectivity of the pores of the membrane body after being extracted by water, thereby realizing the adjustment of the microstructure of the membrane.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1:
s1, taking 20 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 2 parts of polyvinylpyrrolidone (with the weight average molecular weight of 3.1 ten thousand), 77.9 parts of dibutyl sebacate and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at 130 ℃, cooling the mixture particles for 15 seconds through air, cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature absolute ethyl alcohol, fully washing the porous membrane for 1 hour each time to remove dibutyl sebacate and polyvinylpyrrolidone, taking out the porous membrane and airing the porous membrane, and then placing the porous membrane in an oven at 80 ℃ for heating and shaping for 10 minutes to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 360L/m2h, the average pore diameter of the membrane is 20 nm. The membrane pure water flux of the corresponding unblended polyvinylpyrrolidone is 31L/m2h, the average pore diameter of the membrane is 20 nm.
Example 2:
s1, taking 30 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 10 parts of polyvinylpyrrolidone (with the weight average molecular weight of 4.5 ten thousand), 59.9 parts of dibutyl sebacate and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at the temperature of 140 ℃, cooling the mixture particles for 30 seconds through air, cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature absolute ethyl alcohol, fully washing the porous membrane for 1 hour each time to remove dibutyl sebacate and polyvinylpyrrolidone, taking out the porous membrane and airing the porous membrane, and then placing the porous membrane in an oven at 80 ℃ for heating and shaping for 10 minutes to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 9680L/m2h, the average pore diameter of the membrane is 300 nm. The membrane pure water flux of the corresponding unblended polyvinylpyrrolidone is 9L/m2h, the average pore diameter of the membrane is 30 nm.
Example 3:
s1, taking 20 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 2 parts of polyvinylpyrrolidone (with the weight average molecular weight of 3.1 ten thousand), 77.9 parts of tributyrin and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at the temperature of 150 ℃, cooling the mixture particles for 15 seconds through air, cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature absolute ethyl alcohol, fully washing the porous membrane for 1 hour each time to remove the tributyrin and the polyvinylpyrrolidone, taking out the porous membrane and drying the porous membrane in the air, and then placing the porous membrane in an oven at 80 ℃ for heating and setting for 10min to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 270L/m2h, the average pore diameter of the membrane is 15 nm. The membrane pure water flux of the corresponding unblended polyvinylpyrrolidone is 31L/m2h, the average pore diameter of the membrane is 20 nm.
Example 4:
s1, taking 20 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 2 parts of polyvinylpyrrolidone (with the weight average molecular weight of 3.1 ten thousand), 77.9 parts of ethylene carbonate and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at the temperature of 150 ℃, cooling the mixture particles for 15 seconds through air, cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature deionized water, fully washing the porous membrane for 1 hour each time to remove the ethylene carbonate and the polyvinylpyrrolidone, taking out the porous membrane and drying the porous membrane in the air, and then placing the porous membrane in an oven at 80 ℃ for heat setting for 10min to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 230L/m2h, average membrane pore diameter of 10nAnd m is selected. The membrane pure water flux of the corresponding unblended polyvinylpyrrolidone is 31L/m2h, the average pore diameter of the membrane is 20 nm.
Example 5:
s1, taking 30 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 2 parts of polyethylene glycol (with the weight average molecular weight of 1000), 67.9 parts of ethylene carbonate and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at the temperature of 150 ℃, cooling the mixture particles for 15 seconds through air, cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature deionized water, fully washing the porous membrane for 1 hour each time to remove the ethylene carbonate and the polyethylene glycol, taking out the porous membrane and drying the porous membrane in the air, and then placing the porous membrane in an oven at 80 ℃ for heating and setting for 10min to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 160L/m2h, the average pore diameter of the membrane is 5 nm. The pure water flux of the membrane of the corresponding unblended polyethylene glycol is 31L/m2h, the average pore diameter of the membrane is 20 nm.
Example 6:
s1, taking 30 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 2 parts of polyethylene glycol (with the weight average molecular weight of 20000), 67.9 parts of ethylene carbonate and 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at the temperature of 150 ℃, cooling the mixture particles through air for 30S, then cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature deionized water, fully washing the porous membrane for 1 hour each time to remove the ethylene carbonate and the polyethylene glycol, taking out the porous membrane and drying the porous membrane in the air, and then placing the porous membrane in an oven at 80 ℃ for heating and setting for 10min to obtain the final porous membrane product.
The pure water flux of the membrane was determined to be 710L/m2h, the average pore diameter of the membrane is 25 nm. The pure water flux of the membrane of the corresponding unblended polyethylene glycol is 31L/m2h, the average pore diameter of the membrane is 20 nm.
Example 7:
s1, taking 30 parts of polyvinylidene fluoride (with the weight average molecular weight of 33.7 ten thousand), 10 parts of polyethylene glycol (with the weight average molecular weight of 20000), 59.9 parts of ethylene carbonate and 1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate according to the parts by weight, fully mixing in a mixer, extruding by an extruder, and cooling and granulating in air to obtain mixture particles;
s2, conducting film scraping on the obtained mixture particles through an extruder at 100 ℃, cooling the mixture particles through air for 30S, then cooling the mixture particles in water at room temperature, further forming the mixture particles, and then coiling the mixture particles;
and S3, soaking and washing the porous membrane for 2 times by using room-temperature deionized water, fully washing the porous membrane for 1 hour each time to remove the ethylene carbonate and the polyethylene glycol, taking out the porous membrane and drying the porous membrane in the air, and then placing the porous membrane in an oven at 80 ℃ for heating and setting for 10min to obtain the final porous membrane product.
The pure water flux of the membrane is measured to be 8760L/m2h, the average pore diameter of the membrane is 260 nm. The pure water flux of the membrane of the corresponding unblended polyethylene glycol is 31L/m2h, the average pore diameter of the membrane is 20 nm.
The preparation method and the product thereof for improving the pore penetration and flux of the polymer film by curing the water-soluble high molecular weight polymer to form the template agent in the quenching process are described by examples, and the related technical personnel can obviously modify or appropriately change and combine the contents described herein to realize the invention without departing from the contents, the spirit and the scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention. For example, the types of the polymer or the diluent, the spinning temperature, the type and the temperature of the quenching agent bath, the temperature and the length of the air gap, the type and the addition amount of the water-soluble high molecular weight polymer, different membrane shapes such as a roll type, a hollow fiber and a tube type, a flat composite membrane scraped on a high-temperature resistant non-woven fabric and the like are changed.
Claims (5)
1. A method for simply preparing a porous membrane with excellent penetration is characterized by comprising the following specific steps:
s1, taking a fluorine-containing polymer, a water-soluble high molecular weight polymer, a diluent and an antioxidant, wherein the mass ratio of the fluorine-containing polymer to the water-soluble high molecular weight polymer to the diluent to the antioxidant is 20-30: 2-10: 59.9-77.9: 0.1-1, mixing in a mixer, extruding by an extruder, and cooling in air for granulation;
the fluorine-containing polymer is a homopolymer or a copolymer of polyvinylidene fluoride;
the water-soluble high molecular weight polymer is one of polyvinylpyrrolidone or polyethylene glycol with molecular weight not less than 1000;
the diluent is one of dibutyl sebacate, tributyrin or ethylene carbonate organic matters;
s2, melting the obtained mixture particles and scraping the mixture particles into a film at the temperature of 100-150 ℃, cooling and solidifying the film by air, and then further cooling and forming the film in water at room temperature; the film scraping speed of the scraped film is 10mm-2m/min, and the film is cooled in the air for 15-30S;
and S3, taking out the film, soaking and washing the film by using a room-temperature extracting agent, washing to remove the diluent and the water-soluble high-molecular-weight polymer, taking out the film, airing, and carrying out heat setting treatment.
2. The method for easily producing a porous membrane having excellent permeability according to claim 1, wherein: step S1, the mass ratio of the fluorine-containing polymer, the water-soluble high molecular weight polymer, the diluent and the antioxidant is 25: 6: 68.9: 0.5.
3. the method for easily producing a porous membrane having excellent permeability according to claim 1, wherein: and the antioxidant in the step S1 is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
4. The method for easily producing a porous membrane having excellent permeability according to claim 1, wherein: in the step S3, the extractant is absolute ethyl alcohol or deionized water, and the washing times are 2 times, and each time lasts for 1 hour.
5. The method for easily producing a porous membrane having excellent permeability according to claim 1, wherein: and S3, heating and setting the temperature to be 80-130 ℃ for 10-30 min.
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| CN104474921A (en) * | 2014-12-04 | 2015-04-01 | 贵州省材料产业技术研究院 | Polyolefin porous membrane with perforated honeycomb pore structure and preparation method thereof |
| CN105478021A (en) * | 2016-01-13 | 2016-04-13 | 浙江东洋环境工程有限公司 | Preparation technology of PVDF (polyvinylidene fluoride) microporous membrane |
| CN106582323A (en) * | 2016-11-29 | 2017-04-26 | 康命源（贵州）科技发展有限公司 | Preparation method of high-strength, high-throughput polyvinylidene fluoride hollow fiber membrane and product thereof |
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